Manufacture of imidazolines containing at least 10 carbon atoms



Patented Apr. '25, 1939 MANUFACTURE OF mm TAINING AT LEAST 10 canon a'rom No Drawing. Orl

November 113, 1937, Austria April 4, 1936 Azomrms conginal application huguat 3, 1986, Serial No.- 94,120. Divided and this application Serial No. 174,400. In

a cam (01. zoo-s09) The present invention relates to themanui'acture of imidazolines containing at least 10 carbon atoms.

This application, is

application Ser. No. 94,120, filed August 3, 1936,

in the name of Edmund Waldmann and August Chwala. for Manufacture of imidazolines contaming at least carbon atoms".

We have found that imidazolines containing 10 aliphatic radicals oiv high molecular weight as substitutents at the 2-carbon atom may be obtained by heating with a fatty acid or a carboxylic acid or high molecular weight tohigh temperatures, preferably. to temperatures lying be- 18 tween 200 the one hand of a base having a primary amino, group and a second. primary or secondary amino group, which are in 1,2-position to each other,

1,2-position being linked.

the-two carbon atoms in 20 by a single bond, and on the other hand a salt of such base formed from a strong acid.

Suitable bases having and a second primary or in 1,2-position to each other are ethylene-diamine: products such as diethylene-triamine, triethylene tetramine, tetraethylener pentamine; homologues' of ethylene-diami'ne such as 1,2-propylene-diamine, 2,3-butylene-diamine, N-methylv ethylene-diamine. Suitable strong acids for forming the salts are in particular mineral acids, such as hydrochloric acid, hydrobromic acid, sulfuric acid, and the like;

Suitable fatty acids are in general aliphatic acids containing more than 8 carbon atoms, for instance, capryllc acid, lauric acid, stearic acid, palmitic acid, oleic acid, also mixtures of these acids obtainable by saponie i'ying natural fats like olive oil, tallow, palm oil; also cycloaliphatic acids such as naphthenic acids 40 and the like.

' Instead 'ofthe fatty acids there may be used suitable derivatives thereof such as esters, amides, anhydrides or halides; according to the a primary amino group selection of the derivative to be used, the simultaneous use of the free base or theusalt of the base may, if desired, be omitted, for in the case of halides the suitable mixtures leading to the desired result are formed, due to the mineral acid becoming free, in the course of the acylation.

Quite generally, the new process consists in heating with a product selected from the-group consisting of fatty acids of high molecular weight and the salts, amides, halides and esters thereof, a mixture consisting on the one hand of av base which is substituted at two carbon atoms pared. The process C. and 300 0., a mixture consisting on secondary amino groupof high molecular weight an amino group each, one contains two hydroadjacent to each other by of which amino groups n gen atoms and the other at least one hydrogen a division of United States atom, and on the other hand of a salt oi'such base with a strong acid, the heating being carried out at a high temperature.

The procedure may also be such that first of all the salt of the mono-acyl compound is prethen consists in heating to a high temperature a salt formed from astrong acidand such a diamine mono-acylated with a iattyacid 01' high molecular weight, in which the two amino groups are bound to two carbon atoms adjacent to-,each other, one of which amino groups containing two hydrogen atoms and the other at least one hydrogen atom.

In the preferred mode of operating, the mixture made in accordance with the invention is heated to a temperature of 250 C.-290. C. I1, for example, there is used a quantity or lauric acid. ethylene-,diamine andethylene-diamine hydrochloride, the hydrochloride which forms a temperature, even with only gentie' stirring, and

at the same time causes formation of the un-- decyl-imidazoline hydrochloride. This reaction may also be conducted at a temperature lower than 250 C. by heating for a longer period. The use of a vacuum during the second half of the condensation is useful. I

When the condensation to the imidazoline derivative starts from a mixture of fatty acid amine and amine hydrochloride, the three components of the mixture are advantageously selected so that for 1 mol of the fatty acid or its derivative there are at least 1 mol each of the diamine and the salt-like bound mineral acid. In using one mol of lauric acid, therefore, there should be mol of ethylene-diamine and V mol of ethylene-diamine hydrochloride,- corresponding with the equation:

ana

and there is obtained the ylimidazoline.

If as the lauric acid derivative there is chosen with 1 mol of of ethylenethere is obtained the reaction in the sense of the following equation:

already contains in itself per 1 mol of fatty acid 1 mol of ethylene-diamine and 1 mm of hydrochloric acid, it suffices to heat this hydrochloride by itself to about 250 C.-300 C. in order to obtain an excellent yield of the hydrochloride of undecylimidazoline. This reaction can also be carried out with the other mono-acyl derivatives which are obtained from the diamines and the fatty acids of high molecular weight mentioned in paragraphs 2 and 4 of this specification. Under the effect of the amine salt, particularly the hydrochloride, one finds at comparatively high temperature of reaction evidently an elimination of the acid amide at first formed (as may be seen particularly clearly from the example of dilauroyl-ethylenediamine) and then a combination of the eliminated material directly to the imidazoline hydrochloride. Philipps (Journal ofthe Chemical Society of London, 1928', page 2393 and following; Chemisches Zentralblatt 1928, vol. 2, page 2466) is of opinion that the formation of benzimidazoles or lmidazolines from the acyl derivatives of the corresponding diamines by boiling with hydrochloric acid occurs 01 itself in such a manner that the acid amide is first saponified and the elimina'tedportion united directly to the benzimidazol or imidazoline.

These imidazolines of high molecular weight in the form of their salts are freely soluble in .water; solutions foam and have good capillary active properties. They may be used with advantage for improving dyeings on vegetable fibers.

Sulfo groups may be introduced in their molecules by the methods which have become known from French Specification No. 796,917. These imidazoline sufonates of high molecular weight are also valuable as wetting, foaming, washing, emulsifying and dispersing agents. They vare valuable assistants in the textile industry.

The following examples serve to illustrate the invention, the parts being by weight:

(1) Into a stirring vessel provided with a thermometer and an inverted condenser there are charged y, Parts Stearic acid -1... 284 Ethylene-diamine hydrochloride 93 'Ethylene-diamine hydrate 56 The mixture is heated, while stirring, to C.

and the temperature israised within 90 minutes Parts Lauric acid; Ethylene-diamine hydrate 40 Ethylene-diamine hydrochloride 60 in the manner described in the same example. As soon as a sample of the mass is clearly soluble in water, theheating'is interrupted. 0n cooling, the mass: solidifies in crystalline form; it consists of 2-undecylimidazoline hydrochloride. The base liberated in the usual manner from this salt may be purified byrecrystallization from alcohol of 50 per cent. strength, whereby it is obtained in the form of colorless laminae which melt at 82 C.

(3) In an apparatus such as is described in Example (1) there is heated to 180 C. a mixture of: I i

Parts Oleic acid. Ethylene-diamine hydrate 15 the mass whichat first is somewhat foamy boils finally gently as soon' as the water has been distilled. After cooling to 120 C. there are added another 15 parts of ethylene-diamine hydrate and heating is renewed to C. 37.5 parts of ethylene-diamine hydrochloride are now added, whereupon the temperature of the mass is raised to 280 C. within 15 minutes and kept there for (4) Parts Oleic acid ethyl ester 10 Ethylene-diamine hydrate 2 Ethylene-diamine hydrochloride 3 are heated together in the manner described in Example 1, save that the temperature of the mass for the saponification of the ester is allowed'to remain for some time (about 5-10 minutes) at 120 C.-130 C. The aqueous solution of the heptadecenylimidazoline hydrochloride is treated with some active carbon and the free base is liberated by means of caustic soda; it is obtained in very good yield.

(5) 8.5 parts of N-N-di-lauroylethylene-diamide are heated with 3.3 parts of ethylenediamine hydrochloride in an open flask, while stirring, in such a manner that after 5-10 minutes the mixture has a temperature of about 270 C.280 C. The heating is continued for another-10 minutes to 280' C.-290C.. whereby the greater'quantity of the hydrochloride passes into solution. A sample then dissolves clearly in water.

Caustic soda solution precipitates from the aqueous solution the undecylimidazoline which is the product of reaction in approximately quantitative yield.

(6) 10 parts 01' mono-lauroylethyiene-diamine hydrochloride are heated for 5-10 minutes to 260 (L-280C. and then for a further 5-10 minutes to 285 C.-295 C. The hydrochloride 0! n the undecylimidazoline is thus formed. A smil lar result is obtained by substituting the corresponding hydrobromide orsulfate for the monolauroylethylene-diamine hydrochloride, or by using instead or the mono-lauroyl-ethylene-diamine hydrochloride a derivative aeylated'with by a single bond, one on. which amino-groups contains two hydrogen atoms and the other at least one hydrogen atom.

2. Process for the manufacture of 2-substitutedimidazolines which comprises heating to temperatures lying between 200 C. and 800 C.

a salt formed from a strong acid and such a diamine monoacylated with a fatty acid having at least 8 carbon atoms, in which the two amino groups are bound to two carbon atoms adjacent to each other and linked by a single bond, one

of which amino "groupscontains two hydrogen atoms and the other at least one hydrogen atom.

8. Process for the manufacture of -2-substituted imidazolines which comprises heating to temperatures lyingbetween 200 C. and 300 C. y a salt formed from a strong acid and such a monoacylated with *a fatty acid containing from l0I'to 18 carbon atoms,"i n which the two amino groups are bound to two carbon atoms adJacent to eachother and linked by-a single bond, one oi which amino groups contains two hydrogen atoms'and'the other at least one hydrogen atom. a a v I 4.,Process for the manufacture oi, 2-substituted imidazolines which comprises heating to high temperatures lying between 200 and 300 0., a salt i'ormeci from a strong acid and ethylene-diaminemon'o-acylated with a 'i'atty acid containing from 10 to 18 carbon atoms.

5. Process for the manufacture of 2-substituted imidazolines which comprises heating to temperatures lying between 250 C. and 300 C. j the hydrochloride of ethylene-diamine monoacid containing from 10,

acyiated with a fatt tol8 carbon atoms. 6. Process for the manufacture of the Z-heptadecylimidazoline consisting in heating totemperatures lying between 250 C. and 300 C. the hydrochloride of the ethylene-diamine, monoecylated with'stearic acid.

"I. Process for the manufacture of the Z-heptadecenyiimidazoiine consisting in heating to temperatureslying between 250 C. and 300 C. the

hydrochloride of the ethylene-diamine monoacylated with oleic acid. t V

8. Process for the manufacture of the 2-undecyl-imidazoline consisting in heating to temperatures lying between 250 .C.;and 300 C. the hydrochloride of the ethylene-diamine' monoacylated with lauric acid.

. EDMUND WALDMANN.

AUGUST 'CHWALA. 

